Process for making polymeric products and for modifying polymeric products



Patented it... 2, 19.42

UNITED STATES PATEN MA& I I OLYMERIC PROD- PROCESS FOR 2,284,896 T:OFFICE UCTS AND FOR MODIFYING POLYMERIC PRODUCTS William E. Hanl'ord anmington, Del., assi d Donald F. Holmes, wu-. gnors to E. I. du Pont deNemours 8 Company, Wilmington, Del., a corporation 01' Delaware NoDrawing. Application May 24, 1939, Serial No. 275,539

\ Claims.

preferably in substantially stoichiometric proportions, an organiccompound having a plurality of but preferably two separate and distinctreactive groups of the formula -X=C=Y wherein Xis or N, Y is 0, S, orNR, and R is hydrogen or a monovalent hydrocarbon radical, with an oranic substance having a plurality of groups, each of which containsreactive hydrogen. The reactive hydrogen is that detected and determinedby the Zerewitinofl. method. The products are polymers. When thereactancts are blfunctional, i. e., when one reactant contains twogroups of formula -X=C=Y and the other reactant contains two groups withreactive hydrogen, the products are linear polymers. When one of thereactants is already polymeric, the product is a' modified polymer ofhigher molecular weight.

The more detailed practice of the invention is illustrated by thefollowing examples, wherein parts given are by weight. There are ofcourse many forms of the invention other than these specificembodiments.

Example I of open weave, are more water-repellent than the originalvoile and support drops of water without wetting even after repeatedwashing with acetone or soap.

Other forms of cellulose, e. g., woodand paper, may be treated with acompound containing a plurality of -X=C=Y groups by a similar process toyield improved products.

Example II Fifteen parts by weight of cellulose acetate flake containing54.5 per cent combined acetic acid is dissolved in parts of acetone. Tothis solution there is added 1.5 parts of hexamethylene diisocyanate andthe mixture is agitated promptly to produce a homogeneous solution.

After three hours, an increase in the viscosity of the solution isobserved. Within 24 hours, the solution no longer flows, having changedinto a gel. Evaporation of the acetone yields a hard,

infusible, modified cellulose acetate which is insoluble in both acetoneand pyridine.

' Example III Five linear yards of cellulose acetate tricot" measuring36 inches in width is folded twice in the lengthwise direction andpassed through 1500 g. of a 10 per cent solution of hexamethylenediisocyanate in benzene so as to become completely soaked therewith. Thetricot is then hung in air for about 30 minutes, during which time thebenzene evaporates, leaving the fabric thoroughly impregnated withhexamethylene diisocyanate. The fabric is then wound upon. a piece ofheavy glass tubing and baked for one hour at 140-5 C. The fabric thusproduced is insoluble in acetone and can be thoroughly soaked in thissolvent without any apparent effect except a slight shrinkage. Whenironed with an electric fiat iron at a temperature of 280 0., it doesnot stick to the iron, nor fuse, nor tear into shreds as does anuntreated tricot under the same conditions.

Example IV A 300 meter skein of cellulose acetate yarn denier, 32filaments, 5 turns per inch) is soaked in a 10% solution ofhexamethylene diisocyanate in benzene. After removing the yarn from thesolution and hanging it in air for 20 minutes to permit evaporation ofthe benzene, the yarn is baked for one hour at -5 C. The resultant yarnis insoluble in acetone and shows no apparent swelling. A comparison 01'the properties of the yarn with those of the initially untreatedmaterial is given below:

Other cellulose derivatives containing free hydroxyl groups, e. g.,cellulose butyrate, cellulose nitrate, ethyl cellulose and benzylcellulose, can

also be modified by reaction with a diisocyanate or diisothiocyanate.

mediately with evolution of much heat.

Resins that may be improved by treatment with a diisocyanate or adiisothiocyanate in a similar iashion include, shellac, natural resins,partially hydrolyzed polyvinyl acetate, and other polymers containing aplurality of reactive hydrogens.

Example V dergoes 12.5% less shrinkage than an untreated control.

Improved properties can also be obtained by treating other proteins, e.g., gelatin, silk, zein,

and casein with diisocyanates or diisothiocyanates under these sameconditions. Synthetic polyamides, e. g., those described in U. S.2,071,253 and 2,130,948 can also be modified in this way.

Example VI Films of polyvinyl formal (Eormvar") prepared from a dioxansolution of the resin are treated with various percentages ofdecamethylene diisocyanate and the resultant materials evaluated fortheir water absorption. It is found that as the concentration of thediisocyanate employed is increased from to 25% the water absorptiongradually decreases. Thus, untreated polyvinyl formal under theseconditions absorbs 19.6% of water while similar material treated withdecamethylene diisocyanate (25%) absorbs only 6% of water.

It is possible to treat polyvinyl alcohol and other polyvinyl alcoholderivatives, such as polyvinyl butyral and the polyvinyl ketal ofmenthyl ethyl ketone, in a similar manner. The products after treatmentare less sensitive to water.

Example VII To-a solution of 19 parts of decamethylenediamine in 39parts of m-cresol is added 24.7 parts of decamethylene diisocyanate. Aprecipitate forms at once with considerable evolution of heat. Themixture is then heated at 218 C. whereupon the precipitate dissolves andthe clear solution soon becomes viscous. After hours at 218 C. thesolution is poured into a large volume of ethanol. The polymer,polydecamethylene carbamide, separates as a white solid which is thenthoroughly washed with ethanol. Its melting point is 209-210" C. It isreadily spinnable to long filaments capable of being' cold drawn intooriented fibers.. The intrinsic viscosity of this polymer, determined asdescribed in U. S. 2,130,948, is 0.28. In this and in Example IX, it ispossible to use a hydroxylated solvent since diisocyanates react withamino groups considerably faster than with hydroxyl groups.

Example VIII To a solution of 7.9 parts of hexamethylenediamine in partsof m-cresol is added 11.4 parts of hexamethylene diisocyanate (B. P.ill-112 C./4 mm.).

On heating the mixture, the precipitate all dissolves and a clearsolution is obtained. This solution is heated at 205-210 C. for sevenhours, then diluted with alcohol, whereupon the polymeric A precipitateforms imcarbamide precipitates as a light gray solid. After thoroughwashing with alcohol, the polymer melts at 269-270 C. It can be spuninto filaments which can be cold drawn into oriented filaments.

Example IX A mixture of 39.7 parts of m-phenylene diisocyanate (M. P.50-51 C.) and 26.8 parts of mphenylene diamine is heated in anatmosphere of oxygen-free nitrogen at C. for 30 minutes, then at 180 C.for 4 hours. The mixture is incompletely fused at this temperature; evenat 340 C. a portion of the product remains solid. The polymer is aglassy solid, capable of being drawn into filaments.

Example X To a solution of 7.05 parts of lauryl alcohol in 97.66 partsof decamethylene glycol is added 129.9 parts of decamethylenediisocyanate. The ingredients are thoroughly mixed and heated at 70-80C. for a few minutes. The mixture is then heated for 2- hours at l54-70C. This entire operation is conducted in an atmosphere of dry,oxygen-free nitrogen. The resulting linear poly.- mer, a polyurethane,is colorless and melts at C. It has an'intrinsic viscosity of 0.56 asdefined in U. S. 2,130,948. When molten, the polymer can be drawn intolong fibers which exhibit cold-drawing properties. The purpose of thelauryl alcohol, which contains only one reactive hydrogen, in thisexperiment isto act as a viscosity stabilizing agent, i. e., an agentadded to interrupt the polymerization when a certain degree ofpolymerization has been obtained.

Example XI To 43.31 parts of meta-phenylene diisocyanate is added 31.95parts of hexamethylene glycol in an atmosphere of dry nitrogen. Thismixture is heated at 100 C. for ten minutes, during which time thesolids fuse to a homogeneous liquid which solidifies. This polymer isheated at C. for six hours. When cooled, the resulting product is acolorless, porous, brittle mass, softening at 135 0., melting at 230 C.,and having an intrinsic viscosity of 0.56 as determined in m-cresol.Filaments prepared by touching a cold rod to the molten polymer andwithdrawing the rod have tenacities of 0.6 gram/denier calculated on theoriginal dimensions or 0.8 gram/denier calculated on the breakdimension.

Example XII To 12.70 parts of 2,2-bis(4-hydroxyphenyl) propane '(HOOWQOH) is added 12.48 parts of decamethylene diisocyanate in anatmosphere of dry nitrogen. The mixture is heated for two hours at150-170 C., during which time the reactants meltdown to form ahomogeneous solution which later solidifies. The polymerization iscompleted by heating for two hours at 200 C. The-polymer so prepared isa hard, brittle, almost colorless, transparent product which softens at70 C. and melts at 205 C. It can be transformed into filaments. Thepolymer is insoluble in all common organic solvents.

- amide) Example XIII To 17.98 parts of hexamethylenebis (glycol- (HOcmcumonamnicmon) is added 17.36 parts of decamethylene diisocyanate inan atmosphere of dry nitrogen. The mixture is heated for two hoursat150-170 C., during which time the reactants first melt down to form twoimmiscible layers. Upon agitation the layers form a homogeneous solutionwhich soon solidifies. Polymerization is completed "by heating for twohours at 200 C. The polymer Example XI To 20.17 parts of decamethylenedithiol (HS(CH2)10SH) is added 21.91 parts of decamethylene diisoeyanatein an atmosphere of dry nitrogen. The mixture is heated for two hours at150-170 C., during which time the reactants melt to a, homogeneoussolution which then solidifies. Polymerization is completed by heatingfor two hours at 200 C. The polymerso prepared is hard, white, andopaque. It softens M120" 0. and melts at 130 c. The intrinsic viscosityof the. polymer, as determined in m-cresol,. is 0.35. The product issoluble in hot chlorobenzene or ethylene chlorohydrin.

Anal. Calcd. for (C22H42O2N2S2M: S, 14.89. Found: S, 14.29.

Example XV To 60.54 parts of decamethylene glycol is added 69.57 partsof hexamethylene diisothiocyanate in an atmosphere of dry nitrogen.These, when heated at 125 C., form two immiscible layers which become ahomogeneous solution within fifteen minutes. The reaction mixture isheated a total of one hour at 125 C. and three hours at 200 C. Thepolymer so formed is of a light reddish brown color and, at roomtemperature, is a firm, slightly rubbery resin. The polymer becomesmoldable at 100 C. and melts at 170 C. The product is soluble in hotphenols but insoluble in other common organic solvents.

Anal. Calcd.'for (C1BH34O2N2S2)=2 N, 7.48. Found: N (Dumas), 7.48.

Example XVI To 66.70 parts of decamethylene dithiol (HS(CH2)10SH) isadded 64.72 parts of hexamethylene diisothiocyanate in an atmosphere oi!dry nitrogen. This solution is heated one hour at 125 C. and one hour at200 C. The polymer so prepared is a brown resin, rubbery at roomtemperature. The product becomes moldable at 180 C. and melts at 205 C.The polymeris soluble in hot phenols but insoluble in other commonorganic solvents.

Anal. Calcd. for (C18H34N2S0z! Found: N (Dumas), 6.89.

Example XVII To 7.95 parts of decamethylene diisothiocyanate de- Theseparates aiter a short washed with ether, 12 is insoluble in alcohol,

in 140 parts 01. ether is added 5.34 parts of camethylenediamine in 59parts of ether. white precipitate which time is filtered off and partsbeing obtained. It soluble in m-cresol, melts at C., and is presumably alow polymer. To eil'ect further polymerization, it is dissolved in 15parts oi! cresol and heated eight hours at 200 C., during which timesome hydrogen sulfide is evolved. The cresol solution is washed withalcohol, giving a Product which still melts at 115 C. and which has anintrinsic viscosity of 0.31. When fused, the polymer can be drawn to anelastic filament by touching with a, cold rod and removing the rod. Thepolymer is insoluble in dilute sodium hydroxide, dilute hydrochloricacid, and glacial acetic acid.

Example XVIII To 69.40 parts of adipic acid is added 95.15 parts ofhexamethylene diisothlocyanate in an atmosphere of dry nitrogen. Theseare heated 6 hours at C., 3 hours at175 C., and 20 minutes at 280 C. Thepolymer is a light brown, porous solid melting in a sealed tube atpolyhexamethylene adipamide melts at about 260 C. under the sameconditions. The product of thecondensation hasan intrinsic viscosity of1.14, and, when molten, can be drawn out into a filament by touching themolten mass with a cold rod and withdrawing the rod. The filaments canbe cold drawn. Both the drawn and undrawn filaments show considerablestrength.

Example XIX To 4552 parts of sebacic acid is added 50.49 parts ofdecamethylene diisocyanate in an atmosphere of dry nitrogen. These areheated for 1 hour at 170 C., during which time the reactants dissolveand then solidify. Theheating is continued for 3 hours at 210 C. to 220C., during which time the polymer is molten. The cold product is a hard,tough. cream-colored polymer melting at 189 C. Filaments may be drawn bytouching a cold rod to a molten mass of the polymer and withdrawing therod. The filaments can be cold-drawn. The drawn and undrawn filamentspossess considerable strength.

anate in an atmosphere I are heated for 20 minutes at C. and'then for 45minutes at 150 C. to 280 C. The product is an insoluble polymersoftening at C. and melting at about 320 C.

Anal. Calcd for [CrsI-IzaOzNzh: N, 9.99 Found: N, 9.40.

As additional examples of polybasic acids which may be treated accordingto the process of this invention might be mentioned diphenic acid,citric acid, maleic acid, tartaric acid, terephthalic acid, polyacrylicacid, and polyfumaric acid.

The invention is generically applicable to the reaction of compoundshaving a plurality of groups containing reactivehydrogen, as determinedby the Zerewitinofl method, with a comof dry nitrogen. These anates, aswell as the compounds of mixed functions such as theisocyanate-isothiocyanates, etc.

The preferred compounds are those having two groups of the formula-N=C=Y and of these the diisocyanates and diisothiocyanates in generalare most useful in the practice of this invention and form a preferredsubclass because of their ease of preparation, low cost, reactivity,etc. Additional examples of this subclass are: polymethylenediisocyanates and diisothiocyanates,

such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylenediisocyanate, pentamethylene diisocyanate, etc.; the correspondingdiisothiocyanates; alkylene diisocyanates and diisothiocyanates, such aspropylene-1,2-diisocyanate, butylene-1,2-diisocyanate, butylene-1,3diisocyanate, butylene-2,3-diisocyanate, and butylene-1,3-diiscthiocyanate; alkylidine diisocyanates and diisothiocyanates,such as ethylidene diisocyanate (CH3CH(NCO) 2) butylidene diisocyanatecnacnzcmcmnco) 2 and heptylidene diisothiocyanate (CHaiCHz) CH(CNS) 2)cycloalkylene diisocyanates and diisothiocyanates, such ascyclopentylen'e-1,3 diisocyanate, cyclohexylene-1,2-diisocyanate,cyclohexylene-1,4 diisocyanate, and cyclohexylene-1,2-diisothiocyanate;aromatic diisocyanates and diisothiocyanates, such as m-phenylenediisocyanate, pphenylene diisocyanate, 1-methylphenylene-2,4-diisocyanate, naphthylene-1,4-diisocyanates, 0,0- tolane diisocyanate,diphenyl-4,4'-diisothiocyanate, m-phenylene diisothiocyanate,p-phenylene diisothiocyanate; aliphatic-aromatic diisocyanate ordiisothiocyanates, such as xylylene-1,4-diisocyanate (ocrromQcmnco)xylylene-1,3-diisocyanate OCNCH CHzNCO 4,4'-diphenylenemethanediisocyanate 4, '-diphenylenepropane diisocyanate orxylylene-1,4-diisothiocyanate (s oncm-O-cnmc s) and diisocyanates anddiisothiocyanates containing hetero-atoms, such as SCNCHzOCHzNCS,SCNCH2CH2OCH2CH2NCS, and

In fact. any diisocyanate, diisothlocyanate, or mixedisocyanate-isothiocyanate of the general formula XCNRNCS, in which X isoxygen or sulfur and R is a divalent organic radical, will react withthe, reactive hydrogen compound to give polymers according to thepresent invention.

As examples of additional types of compounds containing two separate anddistinct reactive groups of formula X=C=Y may be mentioned As examplesof compounds containing more than two reactive groups of-formula-'-X=C=Y and of the preferred subclass N=C=Y, there may be mentioned1,2,4-benzene triisothiocyanate and butane-1,2,2-triisocyanate.

While the invention is generic to compounds having a plurality of groupscontaining reactive hydrogen, it may be most conveniently illustrated inrelation to compounds having two such groups as indicated in foregoingExamples VIII-XX. The invention is thus applicable to diols, i. e.,

' to compounds having two hydroxyls, whether phenolic or alcoholic; twosulfhydryls, whether thiophenolic or mercaptan; two amino groups,whether primary or secondary; two carboxyl groups; and to combinationsof these, e. g., compounds having one phenolic and one alcoholichydroxyl group; having one alcoholic hydroxyl group and one mercaptangroup; and having one alcoholic hydroxyl group and one carboxylic orcarbothiolic group.

Additional diols include ethylene glycol, tetramethylene glycol,octamethylene glycol, trlethylene glycol, di(p-hydroxyethyl) ether,resorcinol, p,p'-dihydroxydiphenyl, and N-phenyl diethanolamine.Compounds containing more than two hydroxyl groups may be used asillustrated in Examples I-V and VI. Additional examples of this type areglycerol, sorbitol, triethanolamine, dextrin, and starch.

Additional polythiols include ethylene, trimethylene, hexamethylene,3-methylhexamethylene, p-phenylene and xylylene dimercaptans, 1,2,3-

trithiol propane, 1,2,3-trithiol isobutane, polyvinyl mercaptan,thiolresorcinol, and his (thiol glycolate) (HS-CHy-fll-Q-Clihh O A largenumber of diamines may be used ethylene in place of those mentioned inthe examples, as

for instance polymethylene, alkylene, cycloacetylene dicarboxyiic acid,etc.,

.carboxylic acids those of the HOOCR'COOH, in which R. is nothing or aan integer greater than one, Q is a bivalent group N ,N '-dimethylhexa-N.N'-dimethyldecamethyl- N,N'-dibenzylhexamethylcnediamine,cyclohexyiene-1,4-diamine, o-phenylenediamine, p-phenylenediamine,benzidine, naph- 1 thylene-L4-diamine, -'y,'y'-diaminodibutyl oxide,v-vf-diaminodibutyi sulfide, etc. The preferred diamines are diprimarydiamines in which the amino groups are separated by a hydrocarbonradical containing a chain of at least 4 carbon 1 atoms between theamino groups. However, polyamines having more than two amino groups maybe used, examples being diethylenetriamine and triethylenetetraamine.

Dicarboxylic, dicarbothiolic, and dicarbodithioic acids in general maybe employed, dicarboxylic acids being preferred. Ex-

amples are oxalic acid, malonic acid, polymethylene dicarboxyiic acidssuch as succinie acid, pi-

melic acid, suberic acid, azelaic acid,v decane- 1,10-dicarboxylic acid,etc., unsaturated acids such as maleic acid, itaconic acid (HOOCC(=CH'a) CHIcCOOI-I) dicarboxylic acids such as cyciopentane-Lfl-di-'carboxylic acid, cyclopentane-1,3-dicarboxylic acid.cyclohexane-lJ-dicarboxylic acid, cyclohexane-l,3-dicarboxylic acid,cyclohexane-1,4-

octamethylenediamine, 5

'cycloalkylene 3 dicarboxylic acid, etc, aromatic dicarboxylic acidssuch as phtha1ic'acid, isophthaiic acid, terephthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-1,3-dicarboxylic acid,naphthalene-lA-dicarboxylic acid, naphthalene-1,5-

dicarboxylic. acid, diphenyiene-2,2-dicarboxylic 0 acid,diphenyiene-4,4'-dicarboxylic acid, diphen- -ylene-2,4'-dicarboxyiicacid, etc., aliphatic-aromatic dicarboxyiic acids such asxylylene-1,4-dicarboxylic acid, xyiylene-lB-dicarboxylic acid,

stantially below 100 C. This reaction does not require a hightemperature and in general it is advantageous to operate below 250 C.Modifying agents, such as plasticizers or delusterants, may beincorporated with the reaction mixture.

The polymer may be freed of solvent by direct distillation of thesolvent under reduced pres- 1 sure, or :the polymer may be precipitatedby the addition of a liquid in which it is insoluble, such as methanol,ethanol, acetone or ethyl acetate. it is advantageous in some cases tooperate in a medium in which the polymer is insoluble and from which itseparates as it forms.

In that embodiment of this invention, which involves the use ofmonomeric bifun'ctional reactants, the reactants are heated until theresulting linear polymer exhibitsfiber-forming properties. This stage isreadily determined by a touching the molten polymer with a glass roddicarbothionic, go

and drawing the rod quickly away. If the fiberforming stage is reached afilament of considerable strength and pliability will be formed which iscapable of being cold drawn, that is drawn by applicatilon of tensilestress below its melting point, into fibers which exhibit upon X-rayexamination molecular orientation along the fiber-axis. This process,however, is not limited to the manufacture of the fiber-forming polymersand it is within the scope of this invention to discontinue heatingbefore that stage is reached. The low molecular weight ornonfiber-forming polymers are useful for certain applications, e..g.,molding or coating compositions. Viscosity-stabilized polymers. 1. e.,polymers capable of remaining substantially unchanged in viscosity(molecular weight) under continued conditions of heating as in spinning,film-pressing, or compounding, can be prepared by using as viscositystabilizing agent one reactant in excess of the chemically equivalentamount. Viscosity stabilized polymers may also be prepared by adding asviscosity stabilizing and xylylene-lz-dicarboxylic acid, and acids 5containing hetero-atoms, such as HOOC(CH'.:) aSKCHa) aCOOH etc. In factthere are included as operable digeneral formula 5 divalent radical.Polycarboxylic acids having more than two carboxylic groups, e. g.,citric acid, tricarbaliylic acid, and polyacrylic acid, may also beused.

65 The compounds having a plurality of groups containing reactivehydrogen include but are not limited to compounds" of the formula RKQHM,

R being a polyvalent radical of valence z, :r is

sirable to operate at temperatures not sub- 75 be conducted either agenta small amount of a monofunctional compound reactive with one or otherof the two main reaction components. If fiber-forming products aredesired, not more than about 5 molar per cent of the viscositystabilizing agent should be used It is possible by this process toprepare polymers containing mixed organic radicals by reacting acompound of the formula Y=C=X-R -X=C=Y with a compound of the formulaH-Q-R -Q-H wherein R and R are diiferent organic radicals. Furthermore,it is possible to prepare interpolymers by reacting two or moredifierent compounds of formula HQR -QH with a single compound of theformula process are generally useful for the purposes mentioned inconnection with the polyamides described in U. S. Patents 2,071,250 and2,130,- 948. The more important of these uses are the production ofcontinuous oriented filaments suitable to be used as artificial silk,artificial hair, bristles, threads, ribbons, etc. The polymers are alsoof value as films and as coating agents for cloth, paper, leather, etc.Furthermore, they are well adapted for use in the manufacture of safetyglass interlayers since they are capable of being molded into clear,tough sheets adhering tenaciously to glass.

In these and other uses the polymers may be admixed with other polymers,resins, plasticizers, pigments, dyes, etc. g

The new process described herein permits the preparation of linearpolymers with a wide range of molecular weight. The present invention isfurther advantageous in that it does not require such high temperaturesas most superpolymeric reactions.

When the initial substance reacted with the compound containing theX=C=Y groups is a polymeric product, e. g., cellulose acetate. polyvinylalcohol, or polyacrylic acid, the resulting product is more highlypolymeric than the ori inal polymeric product. This invention provides ameans for effecting cross-linking in linear polymers, such as thosementioned, with the formation of three-dimensional polymers. This iswhat is believed to take place in the reactions described in ExamplesI-VI. The amount of the compound containing the X=C=Y groups necessaryfor this purpose is relatively small. Otherwise the conditions ofpolymerization are essentially the same as for monomeric reactants.Cross-linking with resultant change in properties can be accomplishedwith the use of much less of the compound containing would be requiredto react with all the reactive hydrogens in the polymeric material.

The term "chalcogen is employed by the Committee of the InternationalUnion of Chemistry (J. Am. Chem, Soc. 63, 892 (1941)) as a group namefor the elements oxygen, sulfur, selenium and tellurium. Of these,oxygen and sulfur have an atomic weightless than 33.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

We claim:

1. A process which comprises reacting an organic compound containing, asthe sole reacting groups, a plurality of separate and distinct groupshaving the formula X=C=Y, wherein X is a member of the class consistingof C and N and Y is a member of the class consisting of O, S, and NRwhere R is a member of the class consisting of hydrogen and monovalenthydrocarbon radicals, with an organic substance having a plurality ofgroups containing reactive hydrogen.

2. A process for modifying the properties of polymeric organicsubstances containing a plurality or groups containing reactive hydrogenwhich comprises reacting said substance with an organic compoundcontaining, as the sole reacting group, a plurality of separate anddistinct groups having the formula X=C=Y, wherein X is a member of theclass consisting of C and N and Y. is a member of the class consistingof O, S, and NR where R is a member of the class consisting of hydrogenand monovalen't hydrocarbon radicals.

3. A process which comprises reacting an organic compound having, as thesole reacting groups, a plurality of isocyanate groups with an organicsubstance having a plurality of groups containing reactive hydrogen.

4. A process which comprises reacting an organic compound having, as thesole reactin groups, a plurality of isothiocyanate groups with anorganic substance having a plurality of groups containing reactivehydrogen.

5. A process for modifying the properties of polymeric organicsubstances containing a plurality of groups containing reactive hydrogenwhich comprises reacting said substance with an organic compoundcontaining, as the sole reacting groups, a plurality of isocyanategroups.

6. A process for modifying the properties of polymeric organicsubstances containing a plurality of groups containing reactive hydrogenwhich comprises reacting said substance with an organic compoundcontaining, as the sole reacting groups, a plurality of isothiocyanategroups.

7. Process which comprises reacting an organic substance having aplurality of hydroxyl groups with an organic compound containing, as thesole reacting groups, a plurality of separate and distinct groups havingthe formula X=C=Y, wherein X is a member of the class consisting of Cand N and Y is a. member of the class consisting of O, S, and NR where Ris a member of the class consisting of hydrogen and monovalenthydrocarbon radicals.

8.A process for preparing linear polymers which'comprises reacting anorganic monomeric monohydroxy monocarboxylic acid with an organiccompound having, as the sole reacting groups, two separate and distinctgroups having the formula X=C=Y, wherein X is a member of the classconsisting of -C and N and Y is a member of the class consisting of O,S, and NR where R is a member of the class consisting of hydrogen andmonovalent hydrocarbon radicals. i

9. A process for modifying the properties of polymeric organicsubstances containing a plurality of carboxyl groups which comprisesreacting said substance with an organic compound containing, as the solereacting groups, a plu rality of separate and distinct groups having theformula X=C=Y, wherein X is a member of the class consisting of C and Nand Y-is a member of the class consisting of 0,5, and NR where R is amember of the class consisting of hydrogen and monovalent hydrocarbonradicals.

10. A process for modifying the properties of polymeric organicsubstances containing a plurality of hydroxyl groups which comprisesreacting said substance with an organic compound containing, as the solereacting groups, a plurality of separate and distinct groups having theformula X=C=Y, wherein X is a member of the class consisting of C and Nand Y is a member of the class consisting of O, S, and NR where R is amember of the class consisting of hydrogen and monovalent hydrocarbonradicals.

11. Process which comprises reacting an .organic substance having aplurality of hydroxyl groups with an organic compound having, as thesole reacting groups, a plurality of separate and distinct isocyanategroups.

12. Process for modifying the properties of polyvinyl alcohol whichcomprises reacting the same with an organic polyisocyanate wherein theisocyanate groups are the only reacting groups. 4- 13. Process formodifying the properties of a polymeric organic substance containing aplurality of-hydroxyl groups which comprises reacting the same with anorganic polyisocyanate wherein the isocyanate groups are the onlyreacting groups.

14. A processior modifying the properties of polymeric organicsubstances containing a plurality of carboxyl groups which comprisesreacting said substance with an organic polyisothiocyanate wherein theisothiocyanate groups are' the only reacting group 15. Process whichcomprises reacting an organic substance having a plurality of groupscontaining reactive hydrogen with an organic compound having. aplurality of separate and distinct -NCZ groups, wherein Z is a chalcogenof atomic weight less than 33, the remainder of the molecule of the NCZcompound .being hydrocarbon.

16. Process of claim 15 wherein the organic vcyanate wherein themolecule substance contains a plurality of hydroxyl groups.

17. Process of claim 15 wherein the organic substance contains aplurality of carboxyl groups.

18. Process for modifying the properties of polyvinyl alcohol w chcomprises reacting the same with an organic molecule is hydrocarbonexcept for the isocyanate groups.

19. Process for modifying the properties of polymeric organic substancescontaining a plurality of carboxyl groups which comprises reacting thesame with an organic polyisothiois hydrocarbon except for theisothiocyanate groups.

20. A process for preparing linear polymers which comprises reacting anorganic monomeric monohydroxy monocarboxylic acid with an organiccompound having two separate and distinct -NCZ groups, wherein Z is achalcogen of atomic weight less than 33, the remainder of the moleculeoi the NCZ compound being hydrocarbon.

WILLIAM E. HANFORD. DONALD F. HOLMES.

polyisocyanate wherein the

